Triazinylaminobenzaldehydes

ABSTRACT

Compounds of formula I ##STR1## can be used as optical brighteners.

The invention relates to a method for preparing asymmetrictriazinyl-containing stilbene derivatives.

According to the invention there is provided a process for preparing acompound, in free acid or salt form, of formula I ##STR2## in which R is--NR₅ R₆, --SCH₃, halogen or --OR₅ ; R₁ has a significance of R,independent of R;

R₃ is hydrogen, methoxy, --COOH; sulphonamido; C₁₋₄ alkyl;phenylsulphonyl; --CONH₂ or --CN;

R₄ is hydrogen or methyl;

R₅ is hydrogen or phenyl, unsubstituted or substituted by one or twohalogen, C₁₋₄ alkoxy, sulpho, mono- or di-(C₁₋₄ alkyl)amino or C₁₋₄alkyl groups or is C₁₋₄ alkyl unsubstituted or mono-substituted byhydroxy, C₁₋₄ alkoxy, cyano or --CONH₂,; ##STR3## (CH₂)_(p) --CON(R₁₀)₂; (CH₂)_(p) N(R₁₀)₂ or (CH₂)_(p) N.sup.⊕ (R₁₀)₃ A.sup.⊖ where R₁₀ ishydrogen or C₁₋₄ alkyl, m is an integer from 1 to 10 inclusive, p is aninteger from 1 to 4 inclusive, R_(10a) is hydrogen or methyl and A.sup.⊖is an anion;

R₆ is hydrogen or unsubstituted C₁₋₄ alkyl or C₂₋₄ alkyl substituted byone hydroxy, C₁₋₄ alkoxy, cyano, or --CONH₂ ; ##STR4## (CH₂)_(p)--CON(R₁₀)₂ ; (CH₂)_(p) N(R₁₀)₂ or (CH₂)_(p) N.sup.⊕ (R₁₀)₃ A.sup.⊖where R₁₀, R_(10a), p, A.sup.⊖ and m are as defined above;

or R₅ and R₆ together with the N-atom to which they are attached form asaturated heterocyclic amine group;

comprising reacting a compound, in free acid or salt form, of formula II##STR5## with a compound of formula III ##STR6## where the symbols areas defined above, and where R and/or R₁ is halogen optionally furtherreacting with H-R_(a) where R_(a) is a significance of R other thanhalogen.

Preferably in a process according to the invention, in the compound offormula I, R is R' and R₁ is R₁ ' where R' and R₁ ' are as definedbelow.

Preferably for the reaction of the compound of formula II with that offormula III, the pH is from 3 to 5 inclusive and the temperature ispreferably from -5° to 2° C. inclusive. Where R and/or R₁ (in formulaIII) is halogen and the first (or only) halogen is reacted with H-R_(a),the pH is preferably from 5.5 to 7 inclusive and the temperature ispreferably from 20° to 40° C. Where R and R₁ (in formula III) are bothhalogen and the second halogen group is reacted with H-R_(a), the pH ispreferably 7.5 to 8.5 inclusive and the temperature is preferably 40° to100° C. inclusive.

In this Specification, unless indicated to the contrary, where a symbolappears more than once in a formula its significances are independent ofone another. By the term "halogen" is meant chlorine or brominepreferably chlorine, unless indicated differently. Any substituent thatis capable of being linear or branched is linear or branched unlessindicated otherwise.

Preferably R is R' where R' is --NH₂ ; --N(R₆ ')₂ ; --NHR₅ ', --SCH₃,halogen, ##STR7## OR₈, or a saturated heterocyclic amine group attachedto the triazinyl group through the N-atom; where R₅ ' and R₆ ' aredefined below and R₈ is hydrogen, C₁₋₄ alkyl or C₂₋₄ alkyl substitutedby --OH or C₁₋₄ alkoxy and n is 0, 1 or 2. More preferably R is R" whereR" is --NH(R₅ "), --N(R₆ ")₂, (where R₅ " and R₆ " are defined below) ora saturated heterocyclic amine group attached to the triazinyl groupthrough the N-atom.

Preferably R₁ is R₁ ' where R₁ ' has a significance of R', independentof R'; more preferably R₁ is R₁ " where R₁ " is significance of R"independent of R".

Preferably both groups R and both groups R₁ are the same.

Preferably R is not the same as R₁ on the same triazinyl group.

Preferably in a process according to the invention, in the compound offormula I, R is R' and R₁ is R₁ ' where R' and R₁ ' are as definedabove.

More preferably R is ##STR8## and R₁ is more preferably ##STR9##

Preferred heterocyclic amine groups are unsubstituted morpholino,unsubstituted piperazinyl; unsubstituted N-methyl piperazinyl;unsubstituted pyrrolidinyl and unsubstituted piperidinyl.

Preferably R₃ is R₃ ' where R₃ ' is hydrogen or --COOH. More preferablyR₃ is hydrogen.

Preferably the sulpho group in the stilbene group is ortho to theethylene group.

Preferably R₄ is hydrogen.

Preferably R₅ is R₅ ' where R₅ ' phenyl, unsubstituted or substituted byone or two halogen, C₁₋₄ alkoxy, sulpho or C₁₋₄ alkyl groups or is C₁₋₄alkyl, unsubstituted or monosubstituted by one hydroxy, C₁₋₄ alkoxy orcyano.

More preferably R₅ is R₅ " where R₅ " is phenyl, unsubstituted orsubstituted by one chloro, methyl, methoxy or sulpho group; or is C₁₋₄alkyl or C₂₋₄ hydroxyalkyl. Most preferably R₅ is unsubstituted phenyl.

Preferably R₆ is R₆ ' where R₆ ' is unsubstituted C₁₋₄ alkyl or C₂₋₄alkyl monosubstituted by C₁₋₄ alkoxy, cyano or --CONH₂ or hydroxy;

More preferably R₆ is R₆ " where R₆ " is C₂₋₄ alkyl, unsubstituted ormonosubstituted by hydroxy.

Preferred salt forms include alkali metal salts, alkaline earth metalsalts and ammonium salts.

Further, according to the invention there is provided a process forpreparing a compound in free acid or salt form of formula II comprising:

(a) reacting a compound in free acid or salt form of formula IV##STR10##

where the symbols are defined above; with a compound of formula V##STR11## where R₉ is ##STR12## or --H,

to form a compound in free acid or salt form of formula VI ##STR13## and

(b) reducing the compound of formula VI to form a compound of formulaII.

The compounds of formula V where R₉ is other than hydrogen can beprepared by reacting a compound of formula VII ##STR14## with a compoundof formula VIII

    P(C.sub.1-2 alkoxy).sub.3                                  (VIII)

Compounds of formula V where R₉ is hydrogen are known or may be preparedby known methods from known compounds.

Still further according to the invention there is provided a process forpreparing a compound of formula IV comprising oxidising a compound, infree acid or salt form, of formula IX ##STR15## where the symbols are asdefined above.

Preferably the pH is from 5 to 8 and preferably the temperature is from0° to 100° C. Preferably, potassium permanganate is used as oxidizingagent.

Further, according to the invention, there is provided a compound offormula I, defined above in free acid or salt form with the provisionsthat

(i) at least one group R is --NH--R₅ where R₅ is unsubstituted orsubstituted phenyl; and

(ii) if, on one triazinyl group, one of R and R₁ is anilino and theother is morpholino and, on the other triazinyl group, one of R and R₁is anilino, the other cannot be morpholino; and

(iii) all groups R₃ are hydrogen.

Further, according to the invention, there is provided a compound offormula II defined above in free acid or salt form. Preferably allgroups R₃ are hydrogen. More preferably at least one group R is--NH--R₅, where R₅ is as defined above.

Further, according to the invention there is provided a compound offormula IV defined above in free acid or salt form.

Preferably in the new compounds of formula I the substituents on the twotriazinyl rings are such that the triazinyl rings are not the same.

Compounds of formulae III, VII, VIII and IX are known or can be madefrom known compounds by known methods.

The compounds of formula I are useful as optical brighteners foraddition to detergent compositions and for brightening of textilefabrics and paper. They can be used in the manner disclosed in Example 6of U.S. Pat. No. 3,895,009, the disclosure of which is incorporatedherein by reference.

The invention will now be illustrated by the following Examples in whichall temperatures are in °C.

EXAMPLE 1

The compound of formula 1a ##STR16## can be prepared as follows:

150 g of KMnO₄ are dissolved in 2 l of water. 965 g of the compound offormula 1b ##STR17## are dissolved in 2.5 l of cellosole and 2.5 l ofwater. This mixture is cooled to 0° C. and then the KMnO₄ solution isadded dropwise whilst maintaining the temperature of the mixture at 0°until a sample of the solution when spotted on filter paper shows aslight pink colour. The mixture is filtered from resultant 1000 g of thecompound of formula 1a result which can be recovered by evaporating offthe solvent.

EXAMPLE 2

The compound of formula 2a ##STR18## can be prepared by refluxing 791.2g of nitrobenzyl bromide with 669 g of triethylphosphite in 1000 g ofxylene. The ethylbromide resulting is distilled out. 1000 g of thephosphonate of formula 2a results. Excess triethylphosphite and xylenecan be removed by heating the mixture under vacuum.

503 g of the compound of formula 2a are mixed with 858.6 g of thecompound of formula 1a (defined in Example 1) in 100 g of KOH and 10liters of dimethylformamide.

The reactants are warmed slowly up to 50° C. and stirred for 3 hoursunder nitrogen and are poured onto an equal volume of water. The productthat results is of formula 2b ##STR19## and is filtered off from thesolution.

Alternatively, the compound of formula 2b can be prepared as follows:

162.5 g of a wet cake containing the compound of formula 1a (28%actives) are stirred in 75 ml of dimethylformamide and the slurry ismade just alkaline with sodium carbonate. The reaction is heated toreflux and 117 ml of water are distilled out. 16.4 g of p-nitrotoluene,10 ml of piperidine, 10 ml of pyridine and 50 ml of cyclohexane areadded. The mixture is heated under azeotropic distillation for 48 hours.Cyclohexane is removed by distillation and the reaction is diluted withwater. Pyridine and excess p-nitrotoluene are removed by steamdistillation. The reaction is cooled and the orange crystalline productis filtered off. The yield is 35.8 g of the compound of formula 2b (ayield of 60%).

EXAMPLE 3

The compound of formula 3a ##STR20## can be prepared as follows:

585 g of iron filings are slurried in 1 l of water and 100 g of aceticacid and this is refluxed for 30 minutes. 1170 g of the compound 2b(defined in Example 2) dissolved in 5 l of dimethyl formamide are addedslowly at reflux. The mixture is refluxed for 1 hour and a small amountof caustic soda liquid is added to make the reaction slightly alkalineand the iron is then screened off through "hyflo". The filtrate isconcentrated by distillation under vacuum and the amine is filtered off.

Alternatively reduction may be carried out using sodium sulphide.

EXAMPLE 4

The compound of formula 4a ##STR21## can be prepared as follows:

3449 Parts of methyl ethyl ketone (MEK) in a first vessel are cooled to0° C. 225 Parts of cyanuric chloride is added whilst stirring until itis fully dissolved in the MEK.

1379 Parts of demineralised water are placed in a second vessel and 1379parts of a 50% wet cake of the product of formula 3a (defined in Example3) and isopropanol are added to the water whilst stirring. The resultingslurry is pumped onto the cyanuric chloride solution in the first vesselwhilst maintaining the temperature from -2° C. to +2° C. and the pHbetween 4 and 5 by the addition of 69 parts of sodium bicarbonateportion by portion. When the addition is finished 20 parts of NaOH areadded to bring the pH to 6.5.

113 Parts of aniline are added and 180 parts of a 30% sodium hydroxideand 500 parts of water are slowly added to keep the pH between 6.5 and7. The temperature is allowed to rise. When the reaction is ended andthe temperature has risen to 30° C. with the pH at 6.5, 220 parts ofmorpholine are added and the mixture is heated to 70° C. 12 Parts ofsodium hydrosulphite are added to improve the colour. The mixture isrefluxed and 333.9 parts of MEK are distilled off. The resulting mass iscooled to 50° C. and filtered and washed. The resulting product is thecompound of formula 4a.

EXAMPLES 5 to 11

Compounds of the formula ##STR22## in which the symbols are defined inthe Table below, can be made from appropriate reactants by an methodanalogous to that of Example 4.

                  TABLE                                                           ______________________________________                                        Ex-                                                                           am-                                                                           ple                                                                           No.  R                 R.sub.1                                                ______________________________________                                              ##STR23##                                                                                       ##STR24##                                             6                                                                                   ##STR25##        N(CH.sub.2 CH.sub.2 OH).sub.2                          7    N(CH.sub.3)CH .sub.2CH .sub.2OH                                                                 Cl                                                     8                                                                                   ##STR26##        N(CH.sub.2 CHOHCH.sub.3).sub.2                         9                                                                                   ##STR27##        NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH              10                                                                                  ##STR28##        OCH.sub.3                                              11                                                                                  ##STR29##                                                                                       ##STR30##                                             ______________________________________                                    

We claim:
 1. A compound, in free acid or salt form, of formula IV##STR31## in which R is --NR₅ R₆, --SCH₃, halogen or --OR₅ R₁ has asignificance of R, independent of R;each R₃ independently, is hydrogen,methoxy, --COOH; sulphonamido; C₁₋₄ alkyl; phenylsulphonyl; --CONH₂ or--CN; R₄ is hydrogen or methyl; each R₅, independently, is hydrogen orphenyl, unsubstituted or substituted by one or two halogen, C₁₋₄ alkoxy,sulpho, mono- or di-(C₁₋₄ alkyl)-amino or C₁₋₄ alkyl groups or is C₁₋₄alkyl unsubstituted or monosubstituted by hydroxy, C₁₋₄ alkoxy, cyano orCONH₂ ; ##STR32## (CH₂)_(p) --CON(R₁₀)₂ ; (CH₂)_(p) N(R₁₀)₂) or(CH₂)_(p) N.sup.⊕ (R₁₀)₃ A⊖ where R₁₀ is hydrogen or C₁₋₄ alkyl, m is aninteger from 1 to 10 inclusive, p is an integer from 1 to 4 inclusive,R_(10a) is hydrogen or methyl and A.sup.⊖ is an anion; each R₆,independently, is hydrogen or unsubstituted C₁₋₄ alkyl or C₂₋₄ alkyl,substituted by one hydroxy, C₁₋₄ alkoxy, cyano or --CONH₂ ; ##STR33##--(CH₂)_(p) --CON(R₁₀)₂ ; (CH₂)_(p) N(R₁₀)₂ or (CH₂)_(p) N.sup.⊕ (R₁₀)₃A.sup.⊖ ; or R₅ and R₆ together with the N-atom to which they areattached form an unsubstituted morpholino, unsubstituted piperazinyl,unsubstituted N-methyl piperazinyl, unsubstituted pyrrolidinyl orunsubstituted piperidinyl group.
 2. A compound according to claim 1wherein R is R' where R' is --NH₂, --N(R₆ ')₂, --NHR₅ ', --SCH₃,halogen, ##STR34## OR₈, or a saturated heterocyclic amine group attachedto the triazinyl group through the N-atom and selected from the groupconsisting of unsubstituted morpholino, unsubstituted piperazinyl,unsubstituted N-methyl piperazinyl, unsubstituted pyrrolidinyl andunsubstituted piperidinyl,R₁ is R₁ ' where R₁ ' has a significance of R'independent of R', R₅ ' is phenyl, unsubstituted or substituted by oneor two halogen, C₁₋₄ alkoxy, sulpho or C₁₋₄ alkyl groups or is C₁₋₄alkyl unsubstituted or monosubstituted by hydroxy, C₁₋₄ alkoxy or cyano,R₆ ' is unsubstituted C₁₋₄ alkyl or C₂₋₄ alkyl monosubstituted by C₁₋₄alkoxy, cyano, --CONH₂ or hydroxy, R₈ is hydrogen, C₁₋₄ alkyl or C₂₋₄alkyl substituted by --OH or C₁₋₄ alkoxy, and n is 0, 1 or
 2. 3. Acompound according to claim 1 wherein R is R" where R" is --NHR₅ ",--N(R₆ ")₂ or a saturated heterocyclic amine group attached to thetriazinyl group through the N-atom and selected from the groupconsisting of unsubstituted morpholino, unsubstituted piperazinyl,unsubstituted N-methyl piperazinyl, unsubstituted pyrrolidinyl andunsubstituted piperidinyl,R₁ is R₁ " where R₁ " is a significance of R"independent of R", R₅ " is phenyl, unsubstituted or substituted by onechloro, methyl, methoxy or sulpho group, or is C₁₋₄ alkyl or C₂₋₄hydroxyalkyl, and R₆ " is C₂₋₄ alkyl, unsubstituted or monosubstitutedby hydroxy.
 4. A compound according to claim 1 wherein R is not the sameas R₁.
 5. A compound according to claim 1 wherein R₃ is R₃ ' where R₃ ishydrogen or --COOH.
 6. A compound according to claim 2 wherein R' is notthe same as R₁ '.
 7. A compound according to claim 2 wherein R₃ is R₃ 'where R₃ ' is hydrogen or --COOH.
 8. A compound according to claim 3wherein R" is not the same as R₁ "
 9. A compound according to claim 3wherein R₃ is hydrogen.
 10. A compound according to claim 6 wherein R₃is R₃ ' where R₃ ' is hydrogen or --COOH.
 11. A compound according toclaim 8 wherein R₃ is hydrogen.
 12. A compound according to claim 10wherein R₄ is hydrogen.
 13. A compound according to claim 11 wherein R₄is hydrogen.
 14. The compound according to claim 13 of the formula##STR35##